Glucosinolate aglucones and analogues: insecticidal properties and a QSAR

Naturally occurring aglucones of three glucosinolates (sinigrin, glucotropaeolin, and epi-progoitrin) were tested for fumigation activity against the house fly, Musca domestica, and the lesser grain borer, Rhizopertha dominica. A total of eight natural aglucones were evaluated in the bioassays. Two aglucones of sinigrin showed efficacy against both species which was comparable with that of a commercial fumigant, chloropicrin. None of the aglucones tested was comparable in activity to dichlorvos. Aglucones of glucotropaeolin were also insecticidal, but not to the same level as the sinigrin aglucones. The aglucones of epi-progoitrin were only slightly effective as fumigants. A quantitative structure–activity relationship (QSAR) was developed for synthetic analogues of the sinigrin and glucotropaeolin aglucones. An electronic parameter, σ*, provided the best predictor of activity in R. dominica, whereas a hydrophobicity parameter, π, best predicted activity in M. domestica. © 1998 Society of Chemical Industry     

Quantitative structure-activity relationships of pyrethroid insecticides

The structure-activity relationships of two congeneric series of pyrethroid insecticides, the methylbenzyl (1RS)-cis,trans-chrysanthemates tested against Musca domestica (houseflies) and Phaedon cochleariae (mustard beetles), and the (E)-4-aryl-3-chlorobut-2-enyl chrysanthemates and their corresponding 2,2,3,3-tetramethylcyclo-propanecarboxylates tested against M. domestica only, have been examined using multiple regression analyses and substituent constants. With M. domestica, different optimum partition values (π) were indicated for knockdown and toxicity; with P. cochleariae, an optimum π value for toxicity, similar to that for M. domestica, was obtained 24 h after application, but at later times the more lipophilic compounds were more effective. For the methylbenzyl chrysanthemates, a steric constraint associated with 3,5-dimethyl substitution reduced toxicity approximately five-fold. The influence on toxicity of geometrical isomerism and electronic effects are briefly discussed. Differences between the required polarities for knockdown and toxicity are attributed to variations in the binding affinities of pyrethroid molecules at the sites of action.     

A test for repellency to non-biting flies and a comparison of repellents using Musca domestica L.

A system for testing the effect of a repellent against nonbiting flies attracted to man was developed for Musca domestica L. and Musca vetustissima Walk., and was used to compare the repellency of a range of chemicals against the former. Both arms of one person were simultaneously exposed to large numbers of the test insect in a cage, with repellent applied to a 45 cm² area on one arm, and the solvent to an identical area on the other arm. By varying the dose of repellent, a dose-to-repellency relationship was established and evaluated using probit analysis to determine 50% (RD₅₀) and 90% (RD₉₀) repellency. Both values were required to characterise a repellent. Greatest uniformity of results was obtained with even illumination of the cages from above and exclusion of side lighting. RD₅₀ and RD₉₀ values were not affected by prior exposure of the flies in a cage and did not change with time. Of the repellents tested, dipropyl isocinchomeronate was the most effective against M. domestica. The repellent effect of mixtures of the compounds was tested against M. domestica and was less than expected by summation of the components acting alone, suggesting that to minimise the total dose of chemical applied to skin, single compounds are preferable to mixtures.     

Evaluation of semiochemical toxicity to houseflies and stable flies (Diptera: Muscidae)

BACKGROUND: The housefly, Musca domestica L., and stable fly, Stomoxys calcitrans (L.) are cosmopolitan pests of both farm and home environments. Houseflies have been shown to be resistant to a variety of insecticides, and new chemistries are slow to emerge on the market. Toxicities of selected semiochemicals with molecular structures indicative of insecticidal activity were determined against adults from an insecticide‐susceptible laboratory strain of houseflies. The three most active semiochemicals were also evaluated against recently colonized housefly and stable fly strains. RESULTS: Nineteen semiochemicals classified as aliphatic alcohols, terpenoids, ketones and carboxylic esters showed toxicity to houseflies and stable flies. Rosalva (LC₅₀ = 25.98 µg cm^?2) followed by geranyl acetone and citronellol (LC₅₀ = 49.97 and 50.02 µg cm^?2) were identified as the most toxic compounds to houseflies. Permethrin was up to 144‐fold more toxic than rosalva on the susceptible strain. However, it was only 35‐fold more toxic to the insecticide‐tolerant field strain. The compounds generated high toxicity to stable flies, with LC₅₀ values ranging from 16.30 to 40.41 µg cm^?2. CONCLUSION: Quantification of LC₅₀ values of rosalva, citronellol and geranyl acetone against susceptible housefly and field‐collected housefly and stable fly strains showed that semiochemicals could serve as potent insecticides for fly control programs. Copyright © 2010 Society of Chemical Industry     

Binding activity of substituted benzyl derivatives of chloronicotinyl insecticides to housefly‐head membranes,and its relationship to insecticidal activity against the housefly Musca domestica

Variously substituted benzyl derivatives of chloronicotinyl insecticides were synthesized with a wide range of substituents including halogens, NO₂, CN, CF₃ and small alkyl and alkoxy groups at the ortho, meta and para positions, as well as multiple‐substituted benzyl analogues. Their binding activity to the α‐bungarotoxin binding site in housefly (Musca domestica) head membrane preparations was measured. Among the compounds tested, the activity of the meta‐CN derivative was the highest, being 20–100 times higher than those of imidacloprid, acetamiprid and nitenpyram. The synergized insecticidal activity against houseflies was also measured for selected compounds with the metabolic inhibitor, NIA16388 (propargyl propyl phenylphosphonate). For the nitromethylene analogues, including both benzyl and pyridylmethyl analogues, higher binding activity usually resulted in higher insecticidal activity. © 2000 Society of Chemical Industry     

Multiple Resistance in the Larger House Fly Musca domestica in Germany

Populations of the housefly Musca domestica isolated from farms in different German districts with strong resistance problems were compared to laboratory strains with varying resistance spectra. Resistance against pyrethroids, organophosphates and carbamates was tested using impregnated filter papers, and by topical application using a susceptible housefly strain (origin WHO) for comparison. The multi-resistant fly strains tested had a strong resistance against these insecticide groups, ranging from 37- to >10000-fold for organophosphates and 150- to >6600-fold for pyrethroids. The constituent enantiomer pairs of the α-cyano-pyrethroid cyfluthrin were tested, as was beta-cyfluthrin. With respect to multi-resistant fly strains, the isomers II and IV had the best activity, with LD₅₀ values of 0·012 and 0·014 μg per fly, respectively. In addition, different groups of insect growth regulators (juvenile hormone analogues, chitin synthesis inhibitors and one triazine derivative) were tested in a special larvicidal test. The chitin synthesis inhibitors were quite effective against multi-resistant M. domestica strains except for one strain with strong resistance against chitin synthesis inhibitors, developed after extensive treatments with benzoylphenylureas for several years. The fly strains tested were not resistant against cyromazine. Additionally, the insecticides were combined with the synergists piperonyl butoxide, tributylphosphorotrithioate (DEF) and Cibacron blue and tested against the fly strain with the strongest resistance spectrum (‘Grimm’) in comparison to the susceptible strain (‘WHO-N’). Piperonyl butoxide had the greatest effect on the efficacy of cyfluthrin followed by Cibacron blue and DEF. In a parallel investigation with susceptible and resistant house fly strains, different enzyme activities related with resistance mechanisms were tested, e.g. glutathione S-transferase (3·5-fold) and mixed-function oxidase (2·3-fold). Implications of these results for management of insecticide resistance in M. domestica are discussed.     

Efficacy of vaporised ethyl formate/carbon dioxide formulation against stored‐grain insects: effect of fumigant concentration,exposure time and two grain temperatures

BACKGROUND: The ethyl formate/carbon dioxide (CO₂) formulation Vapormate? is a rapid‐acting fumigant being developed for the control of stored‐grain insects. The effects have been investigated of concentration, exposure times of 1, 3, 24 and 72 h and two grain temperatures, 15 and 25 °C, on its efficacy against mixed‐stage cultures of Sitophilus oryzae (L.) Tribolium castaneum (Herbst) and strongly phosphine‐resistant Rhyzopertha dominica (F.) strain QRD569. RESULTS: High mortalities (≥92%) of mixed‐stage cultures of all three species were obtained when grain was fumigated with the formulation (193 g m^?3 ethyl formate) for 1 h. Complete control of R. dominica QRD569 and T. castaneum was achieved with 63 and 76 g m^?3 ethyl formate respectively, with exposure for 24 h, whereas mean mortality of S. oryzae was 86% under the same conditions. Mortalities of S. oryzae juvenile stages were significantly lower than adults under the conditions tested, which was due to pronounced tolerance of mid‐stage pupae to the fumigant. Reducing grain temperature from 25 to 15 °C had no effect on insect mortality. CONCLUSION: Ethyl formate/CO₂ formulation is highly effective against stored‐grain insects over a range of concentrations and exposure times. Efficacious fumigations were conducted in as little as 1 h, and a strongly phosphine‐resistant R. dominica strain was readily controlled with the fumigant. Copyright © 2009 CSIRO, Australia. Published by John Wiley & Sons, Ltd     

Effects of mode of testing on susceptibility to various insecticides of adults or larvae of Lucilia sericata,Chrysomya putoria and Musca domestica L

Relative potency of eight compounds (four pairs of similar types) to adults and old larvae of three species of cyclorhaphous diptera was determined by injection, oral or topical application. The following points emerged from comparisons of equitoxic doses: (a) C. putoria was consistently more susceptible than L. sericata. M. domestica was more susceptible to organochlorines than either of the blowflies, but less susceptible to organophosphorus, carbamate or pyrethroid insecticides; (b) the most potent insecticides (bioresmethrin, diazinon) were about equally toxic to adults and larvae of all species; but some compounds (especially DDT, gamma-BHC and propoxur) were relatively much less effective against larvae; (c) LD₅₀ values for oral treatments were higher than by injection, and those for contact treatments higher still. These “penetration factors” were highly correlated within each of the stages. This could be due to similarity in the cuticular barrier and (or) detoxication; (d) experiments with various synergistic compounds showed higher synergistic factors for larvae than adults (with DDT, bioresmethrin and propoxur). This probably indicates a more efficient detoxication system in the larvae, which is consistent with findings (b) and (c).     

Efficacy of layer treatment with methoprene for control of Rhyzopertha dominica (Coleoptera: Bostrychidae) on wheat, rice and maize

BACKGROUND: Insect growth regulators are promising alternatives to traditional pesticides in stored grain. The efficacy of the juvenile hormone analogue methoprene was evaluated as a layer treatment in a laboratory experiment for control of Rhyzopertha dominica (F.) (Coleoptera: Bostrychidae) in wheat, rice and maize. RESULTS: Adults of R. dominica were placed in vials containing 33, 26 and 29 g (to a depth of 6.5 cm) of wheat, rice and maize, respectively, that was entirely or partially treated with 1, 5 or 10 mg kg^?1 methoprene. In wheat and rice, the layer treatments were not as effective as the whole‐grain treatment, but there was decreased progeny production as the application rate increased. However, on maize the partial treatments were as effective as the whole‐grain treatment at 5 and 10 mg kg^?1. CONCLUSIONS: The results suggest that partial layer treatments with methoprene can be used to control R. dominica on maize but may not be effective for control of this species on wheat and rice. Copyright © 2011 Society of Chemical Industry     

Proinsecticides effective against insecticide-resistant peach-potato aphid (Myzus persicae (Sulzer))

A range of potential proinsecticides was synthesised and tested against insecticide-susceptible and -resistant clones of Myzus persicae (Sulzer). They were all esters of compounds known to be toxic or pharmacologically active, and were designed to have increased lipophilicity and to be subject to more rapid activation by hydrolysis in resistant than in susceptible aphids due to the increased amount of esterase present in the resistant clones. The most potent toxins were esters of monofluoroacetic acid. When applied topically, the toxicity of these esters to M. persicae was directly proportional to the esterase content of the aphids. Such compounds would not be suitable as commercial insecticides, but the results serve to illustrate the potential benefits of exploiting a resistance mechanism against one class of compounds to render another class more toxic, i.e. to design compounds that show negative cross-resistance. © 1998 SCI     

Insecticidal potency of novel compounds on multiple insect species of medical and veterinary importance

BACKGROUND: Vector‐borne diseases continue to present significant threats to human, animal and plant health. Mosquitoes, houseflies, sand flies and stable flies are well‐known vectors of several human and animal pathogens. The toxicity of selected semiochemicals with molecular structures indicative of insecticidal activity was determined against these insect species with the aim of developing novel insecticides toxic to multiple insect species. RESULTS: Three semiochemicals, namely beta‐damascone, cyclemone A and melafleur, showed remarkable toxicity to three mosquitoes, Aedes aegypti L., Ae. albopictus (Skuse) and Anopheles quadrimaculatus Say, the housefly, Musca domestica L., the stable fly, Stomoxys calcitrans L., and the sand fly, Lutzomyia shannoni (Dyar). The chemicals were equally toxic to several field‐collected permethrin‐tolerant housefly strains. When formulated as 500 mL L^?1 emulsifiable concentrates, the chemicals demonstrated stability and toxicity on filter paper and camouflage military fabrics, with persistence up to 8 days under laboratory conditions. The chemicals were equally effective under field conditions when evaluated on unpainted plywood panels, although a higher dosage was required under field conditions to achieve similar efficacy. CONCLUSION: Laboratory quantification of LC₅₀ values and field efficacy of three semiochemicals as formulated compounds on mosquitoes, houseflies, stable flies and sand flies showed that these semiochemicals could serve as potent insecticides for multiple insect species. Copyright © 2010 Society of Chemical Industry     

Field evaluation of vaporised ethyl formate and carbon dioxide for fumigation of stored wheat

BACKGROUND: Vapormate? is a cylinderised non‐flammable mixture of ethyl formate (16.7% by weight) and carbon dioxide (CO₂) that has been developed as a rapid fumigant of stored grain. Four field trials were undertaken on wheat in 50 t farm silos to demonstrate the feasibility of dynamic application. To assess treatment efficacy, each trial tested mixed stages of Rhyzopertha dominica F. (>11 000), Tribolium castaneum (Herbst.) (>1500) and Sitophilus oryzae (L.) (>13 000) in mesh cages positioned through the centre of the grain bulk and on the grain surface. Ethyl formate and CO₂ concentrations were measured in the silo during fumigation and in ambient air outside the 6 m fumigation zone. Application rates of 420, 660 and 940 g m^?3 of ethyl formate/CO₂ formulation and exposure times of 24, 3 and 72 h, respectively, were examined using wheat of 10.4–11.7% moisture content and grain temperatures between 2 and 32 °C. RESULTS: All life stages of R. dominica and T. castaneum were fully controlled under all conditions tested, and mortality of all life stages of S. oryzae was greater than 98%. CONCLUSION: Dynamic application of vaporised ethyl formate and CO₂ to 50 t silos proved safe to operators and rapidly effective against stored‐grain insects on cold to warm grain. Copyright © 2009 CSIRO, Australia. Published by John Wiley & Sons, Ltd     

Comparative insecticidal activities and metabolic rates of lindane and its hexadeuterio-analog

Hexadeuterio-lindane(γ-BHC-d₆) was several times as toxic as lindane against the mosquito (Culex pipiens pallens), house fly (Musca domestica), German cockroach (Blattella germanica) and American cockroach (Periplaneta americana). The neuroexcitatory activity of these two compounds did not differ. Lindane was considerably synergized by piperonyl butoxide, but lindane-d₆ was not. A large isotope effect was observed in the in vivo breakdown of lindane-d₆. Thus, the intrinsic toxicities of both compounds are equivalent. The difference in insecticidal activity seems to be due to the different rates of detoxifying biodegradation caused by the kinetic deuterium isotope effect.     

Preliminary study of the fumigant toxicity of allyl alcohol to three stored-product insects

The toxicity of allyl alcohol as a fumigant was assessed for adults ofTribolium castaneum (Herbst.),Rhyzopertha dominica (F.) andSitophilus oryzae (L.). Fumigations were carried out in 3.4–1 glass containers at concentrations of 1–15 mg/l for 3 h. The most sensitive species wasS. oryzae and the most tolerant wasT. castaneum. A dose of 15 mg/l for 3 h was lethal to all three species tested. The feasibility of proposing allyl alcohol as a candidate fumigant is discussed. Publication of the Agricultural Research Organization.     

Insecticidal efficacy of fipronil against four stored‐product insect pests: influence of commodity,dose, exposure interval,relative humidity and temperature

BACKROUND: Fipronil is an insecticidal pyrazole that is commonly used as an insecticide in field crops, urban pesticide and veterinary medicine, but there are no reports of its evaluation against stored‐product insects. Three series of laboratory bioassays were conducted to assess fipronil as a potential grain protectant against adults of Sitophilus oryzae (L.), Tribolium confusum Jacquelin du Val, Rhyzopertha dominica (F.) and Prostephanus truncatus (Horn). Factors such as dose (0.01, 0.1, 1 and 10 mg fipronil kg^?1 grain), exposure interval (24 h, 48 h, 7 days and 14 days), temperature (20, 25 and 30 °C), relative humidity (RH; 55 and 65%) and commodity (wheat, maize, barley and paddy rice) were evaluated with regard to their impact on the insecticidal activity of fipronil. Progeny production was assessed after 64 days of exposure. RESULTS: At doses of < 1 mg fipronil kg^?1 grain, efficacy of fipronil was enhanced by an increase in temperature from 20 to 25 °C against S. oryzae or R. dominica for exposures of > 48 h and against T. confusum or P. truncatus for exposures of > 24 h. A further increase in temperature from 25 to 30 °C, although it enhanced efficacy at doses of < 1 mg fipronil kg^?1 grain against S. oryzae at all exposure intervals and against T. confusum after 7 days of exposure, it was negatively associated with efficacy against R. dominica or P. truncatus for exposures of > 24 h. By contrast, increase in RH did not have a significant impact on efficacy of fipronil. Although the performance of fipronil among the tested commodities was species dependent, this substance appeared to be less effective in paddy rice than in barley, maize and wheat. Regardless of the treated commodity, progeny production of all the tested species was almost suppressed with doses higher than 0.1 mg fipronil kg^?1 grain. CONCLUSIONS: Fipronil appeared to be a very effective alternative to the existing substances in stored‐grain protection at doses equal to or higher than 1 mg fipronil kg^?1 grain, and thus these doses require further evaluation in terms of safety for the consumer and residues on stored products. Copyright © 2010 Society of Chemical Industry     

Evaluation of natural diatomaceous earth deposits from south‐eastern Europe for stored‐grain protection: the effect of particle size

BACKGROUND: The use of diatomaceous earths (DEs) provides a promising alternative to the use of contact insecticides in stored‐product IPM. Geographical origin and the physical properties of a given DE may affect its insecticidal activity. In the present study, DE samples were collected from different locations of south‐eastern Europe, and their efficacy was evaluated in the laboratory against Cryptolestes ferrugineus (Stephens) (Coleoptera: Cucujiidae), Sitophilus oryzae (L.) (Coleoptera: Curculionidae) and Rhyzopertha dominica (F.) (Coleoptera: Bostrychidae). In addition, three fractions comprising particles of different size were obtained from each DE sample and assessed with regards to their effectiveness against the above stored‐product insect pests. RESULTS: DE from the Greek region of Elassona was the most effective against C. ferrugineus and S. oryzae, whereas the DE Kolubara 518, mined in the Serbian region of Kolubara, was the most effective against R. dominica. Smaller particles were more effective than larger particles against the three tested species, although significant differences in the efficacy of fractions containing particles of 0–150 µm and particles with sizes of < 45 µm were not always recorded. CONCLUSIONS: Deposits from south‐eastern Europe appeared to be very effective against the tested species, and therefore this region should be further evaluated as a source of development of commercial products. Particle size is a physical property that should always be taken into account during the DE manufacturing process, as it can strongly influence the insecticidal action of a given product. Copyright © 2009 Society of Chemical Industry     

黄冈仓花蝽对几种仓虫的模拟控制研究

在实验室条件下,研究了黄冈仓花蝽(Xylocoris Sp.)对几种主要仓虫的控制效果。结果表明,黄冈仓花蝽对于锯谷盗、长角谷盗、姬粉盗及谷蠹成虫与卵的控制效果均在90％以上,而对于蛀入粮粒内部的谷蠹幼虫无控制效果,对玉米象控制效果较差。     

The Synthesis and Insecticidal Activity of a Series of 2-Aryl-1,2,3-triazoles

Two synthetic routes to 2-aryl-1,2,3-triazoles are outlined. These have been used to synthesise a wide range of compounds of this structural type. Their insecticidal activities were evaluated against a number of veterinary and public health pests. The activity of these compounds is especially good against the housefly (Musca domestica). Structure–activity relationships are discussed particularly in relation to the physical properties of the compounds.     

Novel acetylcholinesterase inhibitors: Synthesis and structure–activity relationships of phthalimide alkyloxyphenyl N,N-dimethylcarbamate derivatives

Based on the multiple binding sites of acetylcholinesterase (AChE), a series of AChE inhibitors: phthalimide alkyloxyphenyl N,N-dimethylcarbamate were designed and synthesized. AChE inhibitory activity and structure–activity relationship of the compounds were researched also. The influence of structural variations on the inhibitory potency was carefully investigated by modifying different alkyloxy chain length and position between phthalimide and phenyl N,N-dimethylcarbamate (PDM). The biological properties of the series were investigated by considering the activity on isolated enzyme. Some of the newly synthesized derivatives, when tested on isolated AChE from head of housefly (Musca domestica), were more active than PDM. The compounds J1, J2 and K1–K8 demonstrated higher inhibitory activity (5- to 404-fold) for AChE than that of PDM. In particular, compound K1 displayed the best AChE inhibition (404-fold higher than PDM), which suggested that phthalimide group of K1 strongly bound at the residues lining the gorge while phenyl N,N-dimethylcarbamate bound at the catalytic site.     

Efficacy of Bacillus thuringiensis Cry3Aa protoxin and protease inhibitors against coleopteran storage pests

BACKGROUND: Environmental impacts and resistance to insecticides pose serious challenges to stored‐product insect and other types of pest control. Insect‐resistant transgenic grain is a potential alternative to fumigants, but candidate control proteins are needed, especially for coleopterans. Therefore, we evaluated the efficacy of a coleopteran‐active toxin, Bacillus thuringiensis Cry3Aa, with or without protease inhibitors, in laboratory feeding assays against coleopteran storage pests. RESULTS: In a comparison of the toxicity of Cry3Aa protoxin towards three species of coleopteran storage pests, Tenebrio molitor L. was found to be most sensitive, Tribolium castaneum (Herbst.) was most refractory and Rhyzopertha dominica F. displayed an intermediate response. For R. dominica, Cry3Aa combined with 3500 mg potato carboxypeptidase inhibitor or 5000 mg aprotinin kg^?1 diet resulted in both delayed development and increased mortality. Potato carboxypeptidase inhibitor and bovine aprotinin reduced the LC₅₀ of Cry3Aa for R. dominica two‐ and threefold respectively. Cry3Aa treatment resulted in fewer progeny from R. dominica, and progeny was further reduced when the protoxin was combined with potato carboxypeptidase inhibitor. CONCLUSIONS: These data support the hypothesis that a combination of Cry3Aa protoxin and protease inhibitors, particularly a potato carboxypeptidase inhibitor, may have applications in control strategies for preventing damage to stored products and grains by coleopteran pests. Published 2011 by John Wiley & Sons, Ltd.